WO2022186208A1 - Film multicouche, récipient, emballage pour culture cellulaire et procédé de production de film multicouche - Google Patents

Film multicouche, récipient, emballage pour culture cellulaire et procédé de production de film multicouche Download PDF

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Publication number
WO2022186208A1
WO2022186208A1 PCT/JP2022/008633 JP2022008633W WO2022186208A1 WO 2022186208 A1 WO2022186208 A1 WO 2022186208A1 JP 2022008633 W JP2022008633 W JP 2022008633W WO 2022186208 A1 WO2022186208 A1 WO 2022186208A1
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WO
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Prior art keywords
multilayer film
methyl
polyolefin
layer containing
pentene
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PCT/JP2022/008633
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English (en)
Japanese (ja)
Inventor
義之 片山
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三井化学株式会社
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Priority to US18/278,147 priority Critical patent/US20240123716A1/en
Priority to CN202280013851.2A priority patent/CN116887984A/zh
Priority to JP2023503868A priority patent/JPWO2022186208A1/ja
Priority to EP22763263.5A priority patent/EP4302997A1/fr
Publication of WO2022186208A1 publication Critical patent/WO2022186208A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M25/00—Means for supporting, enclosing or fixing the microorganisms, e.g. immunocoatings
    • C12M25/02—Membranes; Filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0065—Permeability to gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0094—Geometrical properties
    • B29K2995/0097—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0098—Peel strength; Peelability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers

Definitions

  • the present disclosure relates to multilayer films, containers, cell culture packs, and methods for manufacturing multilayer films.
  • 4-methyl-1-pentene polymer has a bulky functional group, so it has a lower density than other thermoplastic polyolefin multilayer films. Therefore, multi-layer films containing 4-methyl-1-pentene polymer have high permeability to gases such as oxygen gas and carbon dioxide gas, and are being developed as gas-permeable multi-layer films for packaging materials such as fresh foods. (See, for example, Patent Document 1).
  • 4-methyl-1-pentene polymer is known to have a high melting point and releasability. , sometimes referred to as a "4-methyl-1-pentene polymer multilayer film" requires a high heat sealing temperature and has a low heat sealing strength. Therefore, as a method of imparting heat sealability to a 4-methyl-1-pentene polymer multilayer film, another thermoplastic resin such as an olefin polymer multilayer film is added to the 4-methyl-1-pentene polymer multilayer film.
  • a method of laminating a multi-layer film formed by coalescing hereinafter sometimes referred to as an "olefin-based polymer multi-layer film" has been studied (see, for example, Patent Document 2).
  • a multi-layer film obtained by perforating a polypropylene multi-layer film or the like with a laser, a hot needle, or the like to impart gas permeability is also on the market (see, for example, Patent Document 3).
  • Patent Document 1 JP-A-11-301691
  • Patent Document 2 JP-A-2000-189051
  • Patent Document 3 JP-A-2015-224037
  • 4-methyl-1-pentene polymer has high gas permeability.
  • 4-methyl-1-pentene resin is non-polar and has low wettability, so it has releasability. Therefore, 4-methyl-1-pentene resin may be difficult to bond.
  • a multilayer film is produced using 4-methyl-1-pentene resin, and the packaging material produced from the multilayer film may be required to have heat-sealing properties. It has been difficult to obtain sufficient heat seal strength due to the releasability of the resin.
  • multilayer films or laminated multilayer films mainly composed of 4-methyl-1-pentene polymer have a high heat sealing temperature, so when used for multilayer films for perishables, etc., the flavor of the contents is reduced.
  • the heat-sealed portion may leak or break, making it difficult to use in practice.
  • a problem to be solved by an embodiment of the present disclosure is to provide a multilayer film, a container, a cell culture pack, and a method for manufacturing a multilayer film that are excellent in gas permeability and heat sealability at low temperatures.
  • Means for solving the above problems include the following aspects. ⁇ 1> A layer containing a 4-methyl-1-pentene-based polymer and a layer containing a polyolefin, wherein the layer containing the 4-methyl-1-pentene-based polymer and the layer containing the polyolefin are at least The layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin are partially in contact, and the interlayer adhesion strength between the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin is 0.5 N/15 mm or more, and contains the polyolefin at 120 ° C.
  • the polyolefin is an unsaturated carboxylic acid-modified ethylene- ⁇ -olefin copolymer, an ethylene-unsaturated carboxylic acid-based copolymer, an ethylene-vinyl acetate copolymer, a silane-modified ethylene-vinyl acetate copolymer, Either ⁇ 1> or ⁇ 2> containing at least one selected from the group consisting of ionomers of unsaturated carboxylic acid-modified ethylene- ⁇ -olefin copolymers and ionomers of ethylene-unsaturated carboxylic acid-based copolymers 1.
  • a multilayer film according to one.
  • ⁇ 4> The multilayer film according to any one of ⁇ 1> to ⁇ 3>, wherein the layer containing the 4-methyl-1-pentene polymer has a thickness of 5 ⁇ m to 50 ⁇ m.
  • ⁇ 5> The multilayer film according to any one of ⁇ 1> to ⁇ 4>, wherein the layer containing the polyolefin has a thickness of 1 ⁇ m to 15 ⁇ m.
  • At least one surface of the layer containing the 4-methyl-1-pentene polymer is subjected to at least one treatment selected from the group consisting of plasma treatment, corona treatment, ozone treatment, UV treatment and flame treatment.
  • ⁇ 7> The multilayer film according to any one of ⁇ 1> to ⁇ 6>, obtained by extrusion laminating a layer containing a polyolefin onto the layer containing the 4-methyl-1-pentene polymer.
  • ⁇ 8> The multilayer film according to any one of ⁇ 1> to ⁇ 7>, which is an oxygen permeable multilayer film or a carbon dioxide permeable multilayer film.
  • the oxygen permeability is 11,000 mL/m 2 ⁇ day ⁇ atm to 100,000 mL/m 2 ⁇ day ⁇ atm, and the carbon dioxide permeability is 25,000 mL/m 2 ⁇ day ⁇ atm to 250,000 mL.
  • a container comprising the multilayer film according to any one of ⁇ 1> to ⁇ 12>, wherein the layers of the multilayer film containing the polyolefin are heat-sealed to each other for sealing.
  • a cell culture pack comprising the multilayer film according to any one of ⁇ 1> to ⁇ 13>.
  • a method for producing a multilayer film having a heat seal strength of 3 N/15 mm to 15 N/15 mm when heat-sealed with a heat seal is 0.5 N/15 mm or more, and the layers containing the polyolefin are brought into contact with each other at 120 ° C.
  • the surface treatment includes at least one treatment selected from the group consisting of plasma treatment, corona treatment, ozone treatment, UV treatment and flame treatment.
  • the lamination step the polyolefin is subjected to ozone treatment, and the ozone-treated surface of the polyolefin and the surface-treated surface of the base material are brought into contact with each other, and the surface treatment of the base material is performed.
  • the method for producing a multilayer film according to ⁇ 15> or ⁇ 16> which is a step of laminating the polyolefin on the surface subjected to the above.
  • ⁇ 18> The lamination step of any one of ⁇ 15> to ⁇ 17>, wherein the polyolefin is laminated on a base material containing the 4-methyl-1-pentene polymer by extrusion lamination.
  • a method for producing a multilayer film is a method for producing a multilayer film.
  • the object is to provide a multilayer film, a container, a cell culture pack, and a method for manufacturing a multilayer film that are excellent in gas permeability and heat-sealability at low temperatures.
  • a numerical range represented by “to” means a range including the numerical values before and after “to” as lower and upper limits.
  • the "surface” of a member means the “principal surface” of the member unless otherwise specified.
  • adheresion is a concept that includes “adhesion”.
  • multilayer film is a concept that includes not only what is generally called “multilayer film” but also what is generally called “sheet”.
  • the multilayer film of the present disclosure includes a layer containing a 4-methyl-1-pentene-based polymer and a layer containing a polyolefin, and a layer containing a 4-methyl-1-pentene-based polymer and a layer containing a polyolefin. is in contact with at least a portion, the interlayer adhesion strength between the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin is 0.5 N / 15 mm or more, and at 120 ° C., the polyolefin
  • the heat seal strength when the layers are brought into contact with each other and heat sealed is 3 N/15 mm to 15 N/15 mm. Since the multilayer film of the present disclosure includes the above configuration, it is excellent in gas permeability and heat sealability at low temperatures.
  • 4-methyl-1-pentene-based polymers have high releasability and heat resistance, making it very difficult to heat-seal 4-methyl-1-pentene-based polymers.
  • 4-methyl-1-pentene polymer when attempting to heat-seal a 4-methyl-1-pentene polymer, it was difficult to obtain sufficient heat-sealability even at a high temperature of about 250°C. Therefore, it has been difficult to obtain sufficient heat sealability at a low temperature of, for example, about 120°C.
  • the 4-methyl-1-pentene polymer has high releasability and water repellency, it is not easy to laminate another layer such as an adhesive layer.
  • the 4-methyl-1-pentene polymer has excellent gas permeability, but when the thickness of the multilayer film containing the 4-methyl-1-pentene polymer increases, the above excellent gas permeability Often impairs permeability.
  • As a multilayer film including a layer containing a 4-methyl-1-pentene polymer it has been difficult to achieve both gas permeability and low-temperature heat-sealability.
  • the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin are in contact at least partially. In the portion where the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin are in contact, the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin are directly bonded. there is That is, in the multilayer film of the present disclosure, at least a portion of the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin are in direct contact.
  • the area of the portion where the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin are in contact is 50% or more of the total area of the multilayer film. is preferred, 70% or more is more preferred, and 90% or more is even more preferred. In the multilayer film of the present disclosure, it is also preferable that the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin are in contact with each other.
  • a method of direct adhesion for example, a direct lamination method, which will be described later, is exemplified.
  • the thickness of the multilayer film is preferably 10 ⁇ m to 100 ⁇ m, for example. From the viewpoint of gas permeability, the thickness of the multilayer film is, for example, preferably 80 ⁇ m or less, more preferably 70 ⁇ m or less. The thickness of the multilayer film is preferably, for example, 15 ⁇ m or more, more preferably 20 ⁇ m or more, from the viewpoint of maintaining a balance between gas permeability and heat sealability.
  • the multilayer film of the present disclosure includes a layer (also referred to as a 4-methyl-1-pentene layer) comprising a 4-methyl-1-pentene-based polymer.
  • the 4-methyl-1-pentene-based polymer may be a homopolymer of 4-methyl-1-pentene, or a copolymer of 4-methyl-1-pentene and other monomers. .
  • the copolymer of 4-methyl-1-pentene and other monomer the 4-methyl-1-pentene polymer (A1) described below is preferable.
  • 4-methyl-1-pentene-based polymer (A1) is a structural unit derived from 4-methyl-1-pentene, ethylene or an ⁇ -olefin having 3 to 20 carbon atoms (however, 4-methyl-1- excluding pentene).
  • 4-methyl-1-pentene when the total of structural units derived from 4-methyl-1-pentene and structural units derived from ethylene or an ⁇ -olefin having 3 to 20 carbon atoms is 100 mol% may be in the range of 60 mol % to 99 mol %, preferably in the range of 65 mol % to 98 mol %, more preferably in the range of 65 mol % to 97 mol %.
  • ethylene or ⁇ -olefins having 3 to 20 carbon atoms include linear or branched ⁇ -olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functionalized vinyl compounds, and the like. included.
  • linear or branched ⁇ -olefins examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene.
  • the linear ⁇ -olefin may have 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms.
  • the branched ⁇ -olefin preferably has 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms.
  • cyclic olefins examples include cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, vinylnorbornene, and vinylcyclohexane. Cyclic olefins may have from 4 to 20 carbon atoms, preferably from 5 to 15 carbon atoms.
  • aromatic vinyl compounds include styrene; ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene mono- or polyalkylstyrene;
  • conjugated dienes examples include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3- Conjugated dienes such as octadiene can be mentioned.
  • the conjugated diene may have 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms.
  • Non-conjugated polyenes include, for example, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl- 1,4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropyl Lidene-2-norbornene, 6-chloromethyl-5-is
  • Examples of functionalized vinyl compounds include hydroxyl group-containing olefins; halogenated olefins; unsaturated carboxylic acids such as nonenoic acid and 9-decenoic acid; unsaturated amines such as allylamine, 5-hexeneamine and 6-heptenamine; (2,7-octadienyl)succinic anhydride, pentapropenylsuccinic anhydride, Unsaturated acid anhydrides such as acid anhydrides of the above unsaturated carboxylic acids; Halides of the above unsaturated carboxylic acids; 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene , 7-epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1-nonene, 10-epoxy-1-decene, 11-epoxy-1-undecene and other unsaturated epoxy compounds. be done
  • the hydroxyl group-containing olefin is not particularly limited as long as it is an olefin compound having a hydroxyl group, but is preferably a terminally hydroxylated olefin compound.
  • hydroxyl-terminated olefin compounds include vinyl alcohol, allyl alcohol, hydroxylated-1-butene, hydroxylated-1-pentene, hydroxylated-1-hexene, hydroxylated-1-octene, and hydroxylated-1-decene.
  • hydroxy-1-dodecene hydroxy-1-tetradecene, hydroxy-1-hexadecene, hydroxy-1-octadecene, hydroxy-1-eicosene and other hydroxylated ⁇ -olefins; hydroxy-3-methyl- 1-butene, 4-methyl-1-pentene hydroxide, 3-methyl-1-pentene hydroxide, 3-ethyl-1-pentene hydroxide, 4,4-dimethyl-1-pentene hydroxide, Branched compounds such as 4-methyl-1-hexene hydroxide, 4,4-dimethyl-1-hexene hydroxide, 4-ethyl-1-hexene hydroxide, and 3-ethyl-1-hexene hydroxide and hydroxylated ⁇ -olefins.
  • the hydroxylated ⁇ -olefin may have 4 to 20 carbon atoms, preferably 2 to 10 carbon atoms.
  • the branched hydroxylated ⁇ -olefin preferably has 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms.
  • Halogenated olefins include, for example, halogenated 1-butene, halogenated 1-pentene, halogenated 1-hexene, halogenated 1-octene, halogenated 1-decene, halogenated 1-dodecene, Linear halogenated ⁇ -olefins such as halogenated 1-tetradecene, halogenated 1-hexadecene, halogenated 1-octadecene, and halogenated 1-eicosene; Halogenated-3-methyl-1-butene, Halogenated-4-methyl-1-pentene, Halogenated-3-methyl-1-pentene, Halogenated-3-ethyl-1-pentene, Halogenated-4,4 -Dimethyl-1-pentene, Halide-4-methyl-1-hexene, Halide-4,4-dimethyl-1-hexene, Halide-4-ethyl-1-hexene, Halide
  • the linear halogenated ⁇ -olefin may have from 4 to 20 carbon atoms, preferably from 4 to 10 carbon atoms.
  • the branched halogenated ⁇ -olefin may have from 5 to 20 carbon atoms, more preferably from 5 to 10 carbon atoms.
  • the 4-methyl-1-pentene polymer (A1) may contain only one type of structural unit derived from ethylene or an ⁇ -olefin having 3 to 20 carbon atoms, or may contain two or more types. .
  • Examples of ⁇ -olefins having 2 to 20 carbon atoms other than 4-methyl-1-pentene include ethylene, propylene, 1-butene, At least one selected from the group consisting of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-hexadecene, and 1-octadecene is preferable, and propylene, 1-butene, At least one selected from the group consisting of 1-hexene and 1-octene is more preferred, at least one selected from the group consisting of ethylene, propylene and 1-butene is more preferred, and ethylene and propylene are particularly preferred.
  • the content (mol %) of the structural unit of the 4-methyl-1-pentene polymer (A1) can be measured by the following method.
  • Measuring device Nuclear magnetic resonance device (ECP500 type, manufactured by JEOL Ltd.) Observation nucleus: 13C (125MHz) Sequence: Single pulse proton decoupling Pulse width: 4.7 ⁇ s (45° pulse) Repeat time: 5.5 seconds Accumulation times: 10,000 times or more Solvent: ortho-dichlorobenzene/deuterated benzene (volume ratio: 80/20) mixed solvent Sample concentration: 55 mg/0.6 mL Measurement temperature: 120°C Chemical shift reference value: 27.50 ppm
  • the 4-methyl-1-pentene polymer (A1) has a melting point Tm of 199° C. or less as measured by a differential scanning calorimeter, or a polymer whose melting point Tm is not observed by a differential scanning calorimeter. preferable.
  • the melting point Tm is not observed means that a crystal melting peak having a heat of crystal melting of 1 J/g or more is substantially not observed in the range of -150°C to 200°C.
  • the melting point Tm of the 4-methyl-1-pentene polymer (A1) measured by a differential scanning calorimeter is 199 ° C. or less, or the 4-methyl-1-pentene polymer (A1) is measured by a differential scanning calorimeter.
  • a structural unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (A1), ethylene or 3 to 20 carbon atoms 60 mol of structural units derived from 4-methyl-1-pentene when the total of structural units derived from ⁇ -olefin (excluding 4-methyl-1-pentene) is 100 mol% % to 99 mol %.
  • the melting point Tm of the 4-methyl-1-pentene-based polymer (A1) is 199° C. or less, or the melting point Tm of the 4-methyl-1-pentene-based polymer (A1) is not observed. Multilayer films can be obtained that are moldable and heat-sealable at low temperatures.
  • the melting point Tm of the 4-methyl-1-pentene polymer (A1) is preferably 100° C. to 180° C., or the melting point Tm of the 4-methyl-1-pentene polymer (A1) is not observed. is preferred.
  • the melting point Tm of the 4-methyl-1-pentene polymer (A1) is a value measured by the following method using a differential scanning calorimetry (DSC). About 5 mg of the 4-methyl-1-pentene polymer (A1) was sealed in an aluminum pan for measurement of a differential scanning calorimeter (DSC220C type) manufactured by Seiko Instruments Inc., and heated from room temperature to 10° C./min. to 200°C. In order to completely melt the 4-methyl-1-pentene polymer (A1), it is held at 200°C for 5 minutes and then cooled to -50°C at 10°C/min. After standing at -50 ° C. for 5 minutes, the second heating is performed at 10 ° C./min to 200 ° C. The peak temperature (° C.) in this second heating is the 4-methyl-1-pentene polymer (A1 ) is the melting point Tm. If multiple peaks are detected, the peak detected on the highest temperature side is adopted.
  • DSC220C type a differential scanning calor
  • the 4-methyl-1-pentene polymer (A1) has one or more of the following intrinsic viscosity [ ⁇ ], weight average molecular weight (Mw), melt flow rate (MFR) and density It is preferable to meet the requirements.
  • the 4-methyl-1-pentene polymer (A1) preferably has a limiting viscosity [ ⁇ ] of 0.5 dL/g to 5.0 dL/g measured at 135°C in a decalin solvent, and 0 More preferably 0.5 dL/g to 4.0 dL/g.
  • the intrinsic viscosity [ ⁇ ] of the 4-methyl-1-pentene-based polymer (A1) is within the above range, so the multilayer film becomes less sticky, and extrusion multilayer film molding becomes possible. Become.
  • the intrinsic viscosity [ ⁇ ] is a value measured by the following method using an Ubbelohde viscometer.
  • the weight-average molecular weight (Mw) of the 4-methyl-1-pentene polymer (A1) is preferably 1 ⁇ 10 4 to 2 ⁇ 10 6 from the viewpoint of moldability of the multilayer film, and is preferably 1 ⁇ 10 4 . More preferably ⁇ 1 ⁇ 10 6 . Further, the molecular weight distribution (Mw/Mn) of the 4-methyl-1-pentene polymer (A1) is preferably 1.0 to 3.5 from the viewpoint of stickiness and appearance of the multilayer film. It is more preferably 1 to 3.0.
  • the weight average molecular weight (Mw) of the 4-methyl-1-pentene polymer (A1), and the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) ) is a value calculated by the standard polystyrene conversion method using the following gel permeation chromatography (GPC).
  • Measuring device GPC (ALC/GPC150-Cplus type, integrated differential refractometer detector, manufactured by Waters)
  • GPC ALC/GPC150-Cplus type, integrated differential refractometer detector, manufactured by Waters
  • the melt flow rate (MFR: MeltFlowRate) of the 4-methyl-1-pentene polymer (A1) is preferably 0.1 g/10 min to 100 g/10 min from the viewpoint of fluidity during molding of the multilayer film. , 0.5 g/10 min to 50 g/10 min, more preferably 0.5 g/10 min to 30 g/10 min. Further, when the melt flow rate of the 4-methyl-1-pentene polymer (A1) is within the above range, it is easy to extrude a relatively uniform film thickness.
  • the melt flow rate (MFR) of the 4-methyl-1-pentene polymer (A1) is a value measured at 230° C. under a load of 2.16 kg according to ASTM D1238.
  • the density of the 4-methyl-1-pentene polymer (A1) is preferably 820 kg/m 3 to 870 kg/m 3 and more preferably 830 kg/m 3 to 850 kg/m 3 from the viewpoint of handling. is more preferred. Further, when the density of the 4-methyl-1-pentene-based polymer (A1) is 820 kg/m 3 or more, the mechanical strength of the multilayer film is improved, and the multilayer film is used as, for example, a packaging material. In this case, problems such as brittleness are less likely to occur. When the density of the 4-methyl-1-pentene polymer (A1) is 870 kg/m 3 or less, a multilayer film having higher gas permeability can be obtained.
  • the density of the 4-methyl-1-pentene polymer (A1) is a value measured according to JISK7112 (density gradient tube method).
  • Polymerization catalysts that can be used for the preparation of the 4-methyl-1-pentene polymer (A1) include conventionally known catalysts such as magnesium-supported titanium catalysts, International Publication Nos. 01/53369 and WO01. /27124, JP-A-3-193796, or JP-A-02-41303.
  • the method for producing the 4-methyl-1-pentene polymer (A1) for example, the methods described in International Publication No. 01/27124, International Publication No. 14/050817, etc. can be employed.
  • the thickness of the 4-methyl-1-pentene layer is preferably 5 ⁇ m to 70 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, even more preferably 5 ⁇ m to 40 ⁇ m, further preferably 5 ⁇ m to 5 ⁇ m. 30 ⁇ m is particularly preferred.
  • the 4-methyl-1-pentene layer may further contain a 1-butene polymer (B1).
  • the 1-butene polymer (B1) may be a polymer having structural units derived from 1-butene, structural units derived from ethylene, and structural units derived from propylene. When the total of structural units derived from 1-butene, structural units derived from ethylene, and structural units derived from propylene is 100 mol%, the structural units derived from 1-butene are 5 mol% to It is in the range of 100 mol %. When the structural unit derived from 1-butene is within this range, it is preferable for interlayer adhesive strength.
  • the structural unit derived from 1-butene is more preferably in the range of 50 mol% to 100 mol%, still more preferably 70 mol% to 90 mol%. When the structural unit derived from 1-butene is within this range, it is particularly preferable for interlayer adhesion strength.
  • the structural unit derived from 1-butene is more preferably 5 mol% or more and less than 50 mol%, still more preferably 5 mol% to 35 mol%. in the range. This range of structural units derived from 1-butene is particularly preferable for the transparency of the multilayer film.
  • the structural units derived from ethylene preferably account for 5 mol% to It is in the range of 50 mol %, more preferably in the range of 5 mol % to 30 mol %, still more preferably in the range of 5 mol % to 20 mol %.
  • the structural units derived from propylene preferably account for 5 mol% to in the range of 90 mol%, more preferably in the range of 10 mol% to 80 mol%, still more preferably in the range of 20 mol% to 80 mol%, particularly preferably in the range of 20 mol% to 70 mol% It is in.
  • the content of each structural unit in the 1-butene polymer (B1) can be adjusted, for example, by adjusting the amount of each component added during the polymerization reaction.
  • ethylene and propylene may be used alone or in combination of two. The ratio is not particularly limited.
  • the 1-butene polymer (B1) may be, for example, a polymer obtained by polymerizing 1-butene with at least one of ethylene and propylene. That is, the 1-butene polymer (B1) may be a polymer having no structural units derived from propylene or a polymer having no structural units derived from ethylene.
  • the sum of structural units derived from 1-butene, structural units derived from ethylene, and structural units derived from propylene is usually 90 mol% or more, preferably 95 mol% or more, more preferably 95 mol% or more, of all structural units. is 98 mol % or more, more preferably 100 mol %. That is, the polymer (B1) may have structural units other than structural units derived from 1-butene, ethylene, and propylene within a range that does not impair the effects of the present disclosure. Other structural units include, for example, ⁇ -olefins having 20 or less carbon atoms. Examples include 1-pentene, 1-hexene, 1-octene and 1-decene.
  • the polymer (B1) preferably satisfies the following melt flow rate (MFR) requirements in addition to the above requirements.
  • melt flow rate (MFR) of the polymer (B1) is preferably 0.1 g/10 min to 100 g/10 min, more preferably 0.5 g/10 min to More preferably, it is 50 g/10 min.
  • the melt flow rate (MFR) of the polymer (B1) is a value measured at 230° C. under a load of 2.16 kg according to ASTM D1238.
  • Polymerization catalysts that can be used for the preparation of the polymer (B1) include conventionally known catalysts such as magnesium-supported titanium catalysts, International Publication Nos. WO 01/53369, WO 01/27124, JP-A-3- 193796 or metallocene catalysts described in JP-A-02-41303 are suitable.
  • a method for producing the polymer (B1) for example, the methods described in International Publication No. 2014/042249, International Publication No. 2006/057361, etc. can be employed.
  • the 4-methyl-1-pentene layer may contain a tackifier.
  • tackifiers include liquid polybutene, amorphous polyolefin, aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic-aromatic copolymer hydrocarbon resins, dicyclopentadiene hydrocarbon resins, hydrogenated Aliphatic hydrocarbon resin, hydrogenated aromatic hydrocarbon resin, hydrogenated aliphatic-aromatic copolymer hydrocarbon resin, hydrogenated dicyclopentadiene hydrocarbon resin, synthetic terpene hydrocarbon resin, terpene carbonization Hydrogen resins, hydrogenated terpene-based hydrocarbon resins, coumarone-indene-based hydrocarbon resins, low-molecular-weight styrene-based resins, rosin-based hydrocarbon resins, and the like can be mentioned.
  • tackifier One type of tackifier may be used, or a mixture of two or more types may be used.
  • Commercially available tackifiers include Clearon, trade name, manufactured by Yasuhara Chemical Co., Ltd., and the like.
  • liquid polybutene is preferable as the tackifier from the viewpoint of being able to maintain the gas permeability of the multilayer film to be obtained.
  • the content of the tackifier is preferably more than 0% by mass and 15% by mass or less with respect to 100 parts by mass of the 4-methyl-1-pentene polymer, and is 0.5% by mass to 10% by mass. is more preferable.
  • the content of the tackifier is more than 0% by mass, better interlayer adhesive strength can be obtained.
  • the content of the tackifier is 15% by mass or less, it is possible to prevent the peeling force from becoming excessively large.
  • the kinematic viscosity of the tackifier at 100° C. is preferably 0.02 cm 2 /s to 50 cm 2 /s.
  • the kinematic viscosity is measured and calculated by the method described in JIS K2283.
  • the content of the 4-methyl-1-pentene polymer is preferably 70 parts by mass to 100 parts by mass, and 80 parts by mass to 100 parts by mass. and more preferably 90 parts by mass to 100 parts by mass.
  • a multilayer film of the present disclosure includes a layer that includes polyolefin (also referred to as a polyolefin layer).
  • Polyolefins contained in the polyolefin layer include polyethylene, polypropylene, ⁇ -olefin copolymers, and the like.
  • Polyethylene includes low-density polyethylene, linear low-density polyethylene, and high-density polyethylene.
  • Examples of ⁇ -olefin copolymers include copolymers of two or more monomers selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene and 1-octene.
  • Ethylene- ⁇ -olefin copolymers include, for example, copolymers of ethylene and one or more monomers selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
  • the polyolefins constituting the polyolefin layer one kind may be used alone, or two or more kinds may be used in combination.
  • the polyolefin preferably contains low density polyethylene or linear low density polyethylene.
  • Polyolefins include unsaturated carboxylic acid-modified ethylene- ⁇ -olefin copolymers, ethylene-unsaturated carboxylic acid-based copolymers, ethylene-vinyl acetate copolymers, silane-modified ethylene-vinyl acetate copolymers, unsaturated carboxylic acid copolymers, It also preferably contains at least one selected from the group consisting of ionomers of acid-modified ethylene- ⁇ -olefin copolymers and ionomers of ethylene-unsaturated carboxylic acid copolymers, More preferably, it contains an ethylene-unsaturated carboxylic acid-based copolymer or an ionomer thereof.
  • the ethylene- ⁇ -olefin copolymer used in the unsaturated carboxylic acid-modified ethylene- ⁇ -olefin copolymer may be, for example, a copolymer of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms.
  • ⁇ -olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.
  • the ⁇ -olefin having 3 to 20 carbon atoms is preferably propylene, 1-butene, 1-hexene or 1-octene, and 1-butene, 1-hexene or 1 - is more preferably octene.
  • the molar ratio of ethylene and ⁇ -olefin in the ethylene- ⁇ -olefin copolymer is preferably in the range of 45/55 to 95/5.
  • unsaturated carboxylic acids used for modification include unsaturated carboxylic acids and derivatives thereof.
  • an unsaturated carboxylic acid or a derivative thereof is used, such as maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid , endocis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid), acrylic acid, unsaturated carboxylic acids such as methacrylic acid, or derivatives thereof.
  • the unsaturated carboxylic acid derivatives include acid anhydrides, imides, amides, and esters of unsaturated carboxylic acids.
  • unsaturated carboxylic acid derivatives include maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, and glycidyl maleate.
  • the unsaturated carboxylic acid used for modification is preferably an unsaturated carboxylic acid or an acid anhydride thereof, and more preferably maleic acid, maleic anhydride, nadic acid, and nadic acid anhydride.
  • a method of modifying with unsaturated carboxylic acid a method of performing a graft reaction with unsaturated carboxylic acid can be mentioned.
  • a method for producing a modified product by carrying out graft copolymerization using the unsaturated carboxylic acid or derivative thereof as a graft monomer a conventionally known method can be used. For example, a melt modification method in which an ethylene- ⁇ -olefin copolymer is melted, a graft monomer is added, and graft copolymerization is performed, or an ethylene- ⁇ -olefin copolymer is dissolved in a solvent, a graft monomer is added, and graft copolymerization is performed.
  • a solution denaturation method or the like can be used.
  • radical initiator When carrying out graft copolymerization, it is preferable to carry out the reaction in the presence of a radical initiator from the viewpoint of efficiency.
  • the content of the radical initiator may be in the range of 0.001 to 2 parts by mass with respect to 100 parts by mass of the ethylene- ⁇ -olefin copolymer as the base polymer.
  • Radical initiators include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2 ,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene.
  • the unsaturated carboxylic acid-modified ethylene- ⁇ -olefin copolymer in the present disclosure has a modification amount of 0.01% by mass to 10% by mass with respect to the total amount of the unsaturated carboxylic acid-modified ethylene- ⁇ -olefin copolymer. , preferably 0.1% by mass to 5% by mass, more preferably 1% by mass to 5% by mass.
  • the amount of modification is within the above range, the interlayer adhesion strength between the 4-methyl-1-pentene layer and the polyolefin layer is superior in the multilayer film.
  • the unsaturated carboxylic acid-modified ethylene- ⁇ -olefin copolymer has a melt flow rate (MFR) of 0.05 g/10 minutes or more when measured under conditions of a temperature of 190°C and a load of 2.16 kg according to ASTM D1238. It is preferably in the range of 200 g/10 min, more preferably in the range of 0.1 g/10 min to 100 g/10 min.
  • MFR melt flow rate
  • the unsaturated carboxylic acid-modified ethylene- ⁇ -olefin copolymer may have a crystallinity of 30% or less as measured by X-rays.
  • An ethylene-unsaturated carboxylic acid-based copolymer is a copolymer containing structural units derived from ethylene and structural units derived from an unsaturated carboxylic acid.
  • the ethylene-unsaturated carboxylic acid copolymer in the present disclosure may be a copolymer of ethylene and an unsaturated carboxylic acid, or a copolymer of ethylene, an unsaturated carboxylic acid and other monomers. or a polymer obtained by modifying an ethylene polymer with an unsaturated carboxylic acid.
  • Ethylene-unsaturated carboxylic acid copolymers include ethylene-unsaturated carboxylic acid binary copolymers and ionomers thereof, ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid ester terpolymers and ionomers thereof, ethylene -unsaturated carboxylic acid ester binary copolymers, and from the viewpoint of interlayer adhesive strength and heat seal strength, ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid ester terpolymers and their ionomers are preferred.
  • An ethylene-unsaturated carboxylic acid-based copolymer can be obtained, for example, by subjecting ethylene and an unsaturated carboxylic acid to a radical polymerization reaction under high temperature and pressure in the presence of an organic peroxide or oxygen.
  • Unsaturated carboxylic acids include ethyl acrylate, methacrylic acid, methyl methacrylate, vinyl acetate, vinyl chloride and the like.
  • at least one selected from the group consisting of ethyl acrylate, methacrylic acid, methyl methacrylate, and vinyl acetate is preferable from the viewpoint of excellent heat resistance and high-temperature processing, and ethyl acrylate, methacrylic acid, and methacrylic acid.
  • At least one selected from the group consisting of methyl is more preferred.
  • a copolymer of ethylene and ethyl acrylate (also referred to as EEA in the present disclosure) can be used as the ethylene-unsaturated carboxylic acid copolymer.
  • the content of ethyl acrylate may be 10% by mass to 40% by mass, preferably 15% by mass to 30% by mass, from the viewpoint of moldability and interlayer adhesive strength.
  • the melt flow rate (according to ASTM D1238, measured at a temperature of 190° C. and a load of 2.16 kg) may be 5 g/10 minutes to 50 g/10 minutes, preferably 5 g/10 minutes, from the viewpoint of moldability and interlayer adhesive strength. 10 g/10 minutes to 30 g/10 minutes.
  • ethylene-unsaturated carboxylic acid copolymer a copolymer of ethylene and methacrylic acid (also referred to as EMAA in the present disclosure) can be used.
  • the content of methacrylic acid may be 10% by mass to 40% by mass, preferably 3% by mass to 10% by mass, from the viewpoint of moldability and interlayer adhesive strength.
  • the melt flow rate (according to ASTM D1238, measured at a temperature of 190° C. and a load of 2.16 kg) may be 5 g/10 min to 100 g/10 min, preferably from the viewpoint of moldability and interlayer adhesive strength. 10 g/10 minutes to 80 g/10 minutes.
  • Commercially available products include Nucrel (registered trademark) manufactured by Mitsui-Dow Polychemicals.
  • Ethylene-vinyl acetate copolymer and silane-modified ethylene-vinyl acetate copolymer Ethylene-vinyl acetate copolymer and silane-modified ethylene-vinyl acetate copolymer
  • Ethylene-vinyl acetate copolymer also called EVA
  • a silane-modified ethylene-vinyl acetate copolymer is a compound obtained by modifying EVA.
  • the content of vinyl acetate in EVA is preferably 10% by mass to 50% by mass from the viewpoint of adhesive strength.
  • EVA preferably has a density in the range of 930 kg/m 3 to 980 kg/m 3 .
  • EVA preferably has a melt flow rate (MFR) of 0.8 g/10 minutes to 30 g/10 minutes at 190° C. and a load of 2.16 kg.
  • MFR melt flow rate
  • As the ethylene-vinyl acetate copolymer one produced by a conventionally known method may be appropriately used, or a commercially available one may be used.
  • the silane compound used to modify EVA is preferably an organosilicon compound having one or more unsaturated hydrocarbon groups and one or more alkoxy groups in the molecule.
  • the unsaturated hydrocarbon group include vinyl group, allyl group and (meth)acryl group
  • examples of the alkoxy group include methoxy group, ethoxy group and butoxy group.
  • Preferred examples of the silane compound include vinyltrimethoxysilane and vinyltriethoxysilane, in which the unsaturated hydrocarbon group is a vinyl group and the alkoxy group is a methoxy group or an ethoxy group.
  • the content of the silane compound in the silane-modified EVA is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of EVA.
  • the silane-modified EVA in the present disclosure may be a compound obtained by graft-modifying EVA with a silane compound.
  • silane-modified EVA can be obtained by adding a silane compound and a radical generator to EVA in an extruder, melt-kneading at a temperature and time equal to or higher than the thermal decomposition initiation temperature of the radical generator, and then pelletizing. can be done.
  • the above radical generator is a compound that is decomposed by heating to generate free radicals, and is used as a reaction initiator that chemically bonds the silane compound to EVA.
  • the radical generator one having a half-life of 3 minutes or less at a temperature of 150° C. or less and the melting point of EVA is particularly preferable.
  • radical generator examples include benzoyl peroxide, lauroyl peroxide, t-butyl peracetate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, dicumyl peroxide, and the like. and peroxides of
  • the content of the radical generator may be appropriately adjusted depending on the type of EVA and the amount of silane compound used.
  • the content of the radical generator is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of EVA.
  • a reaction inhibitor such as mercaptan may be added to suppress polymerization between the silane compounds.
  • the polyolefin in the present disclosure preferably has a D hardness of 20 to 80, more preferably 30 to 70, and even more preferably 30 to 55, from the viewpoint of increasing interlayer adhesive strength.
  • the polyolefin layer preferably contains a slip agent.
  • the slip agents are preferably amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid, ariaic acid, or bisamides of these saturated or unsaturated fatty acids. Of these, erucamide and ethylenebisstearamide are more preferred.
  • the content of the slip agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of polyolefin contained in the polyolefin layer.
  • the multilayer film of the present disclosure has a heat seal strength (also referred to as heat seal strength between polyolefin layers in the present disclosure) when the layers containing polyolefin are brought into contact with each other and heat sealed at 120° C. from 3 N/15 mm to 15 N. /15 mm.
  • the heat seal strength between the polyolefin layers is 3 N/15 mm or more
  • the multilayer film of the present disclosure has excellent heat sealability at low temperatures. From the above viewpoint, the heat seal strength between the polyolefin layers is preferably 3 N/15 mm or more.
  • Heat seal strength is measured by the following method.
  • two multilayer films containing a layer containing the 4-methyl-1-pentene polymer and a layer containing the polyolefin are prepared.
  • the polyolefin layers in the multilayer film are opposed to each other and heat-sealed with a seal bar width of 5 mm at a heat-sealing temperature of 120° C., a pressure of 0.2 MPa, and a sealing time of 1 second, and then heat is released.
  • a 15 mm wide test piece is cut from the test piece obtained by heat sealing, and the peel strength is measured when the heat sealed portion is peeled off at a crosshead speed of 300 mm/min.
  • the thickness of the polyolefin layer is preferably 1 ⁇ m to 15 ⁇ m, more preferably 3 ⁇ m to 15 ⁇ m, even more preferably 5 ⁇ m to 10 ⁇ m, from the viewpoint of maintaining a balance between gas permeability and interlayer adhesive strength of the multilayer film. preferable.
  • the shape of the polyolefin layer is not particularly limited, but it is preferable that the surface of the polyolefin layer is uneven.
  • the unevenness formed on the surface of the polyolefin layer can improve the handleability. Texture can also be imparted to the multilayer film.
  • the multilayer film of the present disclosure has an interlayer adhesive strength of 0.5 N/15 mm or more between the 4-methyl-1-pentene layer and the polyolefin layer.
  • the interlayer adhesive strength is 0.5 N/15 mm or more, the multilayer film of the present disclosure has excellent heat sealability.
  • the interlayer adhesive strength between the 4-methyl-1-pentene layer and the polyolefin layer is preferably 1.0 N/15 mm or more, more preferably 1.5 N/15 mm or more. More preferably, it is 0 N/15 mm or more.
  • the interlayer adhesive strength between the 4-methyl-1-pentene layer and the polyolefin layer There is no particular upper limit for the interlayer adhesive strength between the 4-methyl-1-pentene layer and the polyolefin layer.
  • the interlayer adhesion strength between the 4-methyl-1-pentene layer and the polyolefin layer may be 0.5 to 20.0 N/15 mm or less, and 0.6 to 10.0 N /15 mm or less.
  • the interlayer adhesive strength is measured by the following method.
  • a test piece with a width of 15 mm is cut out from the multilayer film (laminate), and the interlayer adhesion strength is measured using a tensile tester (for example, Autograph AG-X manufactured by Shimadzu Corporation) in accordance with JIS Z1707:1997.
  • the inter-layer adhesion strength is measured between the 4-methyl-1-pentene layer and the polyolefin layer in the test piece under the conditions of a distance between chucks of 90 mm and a tensile speed of 500 mm/min.
  • the multilayer film of the present disclosure may be an oxygen permeable multilayer film or a carbon dioxide permeable multilayer film.
  • An oxygen permeable multilayer film means a multilayer film having an oxygen permeability of 1000 mL/m 2 ⁇ day ⁇ atm or more.
  • a carbon dioxide permeable multilayer film means a multilayer film having a carbon dioxide permeability of 3000 mL/m 2 ⁇ day ⁇ atm or more.
  • the moisture permeability of the multilayer film of the present disclosure (in accordance with JIS Z0208, test temperature 40°C, test humidity 90%), when storing fruits and vegetables, flowers, seedlings, microorganisms, etc., from the viewpoint of preventing the generation of mold, etc. It is preferably 10 g/m 2 ⁇ day to 80 g/m 2 ⁇ day, more preferably 25 g/m 2 ⁇ day to 70 g/m 2 ⁇ day.
  • the oxygen permeability in the multilayer film of the present disclosure is preferably 1000 mL/m 2 ⁇ day ⁇ atm to 100000 mL/m 2 ⁇ day ⁇ atm, more preferably from the viewpoint of long-term storage of fruits and vegetables, flowers, microorganisms, etc.
  • the combination of the upper limit and the lower limit of the oxygen permeability can be appropriately selected.
  • the oxygen permeability of the multilayer film of the present disclosure is preferably 11,000 mL/m 2 ⁇ day ⁇ atm to 100,000 mL/m 2 ⁇ day ⁇ atm, and 11,000 mL/m 2 ⁇ day ⁇ atm to 85,000 mL/m 2 ⁇ It is more preferably 11000 mL/m 2 ⁇ day ⁇ atm to 80000 mL/m 2 ⁇ day ⁇ atm.
  • the carbon dioxide permeability of the multilayer film of the present disclosure is preferably 8000 mL/m 2 ⁇ day ⁇ atm to 250000 mL/m 2 ⁇ day ⁇ atm from the viewpoint of long-term storage of fruits and vegetables, flowers, microorganisms, etc.
  • the multilayer film of the present disclosure preferably has a carbon dioxide permeability of 25,000 mL/m 2 ⁇ day ⁇ atm to 250,000 mL/m 2 ⁇ day ⁇ atm, more preferably 25,000 mL/m 2 ⁇ day ⁇ atm to 230,000 mL/m 2 . ⁇ It is more preferable that it is 25000 mL/m 2 ⁇ day ⁇ atm ⁇ 20000 mL / m 2 ⁇ day ⁇ atm, more preferably 25000 mL / m 2 ⁇ day ⁇ atm ⁇ 15000 mL / m 2 ⁇ day - Atm is also particularly preferred.
  • the hydrogen permeability of the multilayer film of the present disclosure is preferably from 10,000 mL/m 2 ⁇ day ⁇ atm to 300,000 mL/m 2 ⁇ day ⁇ atm, more preferably 50,000 mL/m 2 ⁇ day ⁇ atm to 230,000 mL/m 2 ⁇ day ⁇ atm, still more preferably 50,000 mL/m 2 ⁇ day ⁇ atm to 200,000 mL/m 2 ⁇ day ⁇ atm, Particularly preferably, it is 50000 mL/m 2 ⁇ day ⁇ atm to 150000 mL/m 2 ⁇ day ⁇ atm.
  • the multilayer film of the present disclosure has an oxygen permeability of 2500 mL/m 2 ⁇ day ⁇ atm to 85000 mL/m 2 ⁇ day ⁇ atm and a carbon dioxide permeability of 8000 mL/m 2 ⁇ day ⁇ atm to 250000 mL/m 2 ⁇ day ⁇ atm, and the hydrogen permeability is preferably 10000 mL/m 2 ⁇ day ⁇ atm to 300000 mL/m 2 ⁇ day ⁇ atm.
  • Oxygen permeability (unit: mL/m 2 ⁇ day ⁇ atm), carbon dioxide permeability (unit: mL / m 2 ⁇ day ⁇ atm) and hydrogen permeability (unit: mL / m 2 ⁇ day ⁇ atm) of the multilayer film ) can be measured by JIS K7126-1 (differential pressure method), JIS K7126-2 (equal pressure method), and the like.
  • JIS K7126-1 differential pressure method
  • JIS K7126-2 equal pressure method
  • the hydrogen permeability (unit: mL/m 2 ⁇ day ⁇ atm) of the multilayer film is measured according to JIS K7126-2 by the following method.
  • Measuring device Isobaric gas permeability measuring device (GTR-10XFKS manufactured by GTR Tech Co., Ltd.) Test piece: 50 mm ⁇ Detector; gas chromatography test gas; hydrogen measurement temperature; 23°C Transmission area; 35mm ⁇
  • the moisture permeability (unit: g/m 2 ⁇ day) of the multilayer film is measured by the following method.
  • Moisture permeability is measured in accordance with JIS Z0208 isobaric method (cup type-weight method), using anhydrous calcium chloride as a moisture absorbing material, under the conditions of a test temperature of 40 ° C and a test humidity of 90% RH, and a multilayer film measuring area of 50 cm 2 . and measure.
  • the multilayer film is placed in a constant temperature and humidity apparatus, and the mass is measured (in units of 0.1 mg) for 10 days as a guideline at which the mass increase becomes almost constant at 24 hour intervals, and the moisture permeability is calculated.
  • the total haze in multilayer films of the present disclosure is between 0.1% and 10.0%, preferably between 0.1% and 9.5%.
  • the total haze is in the above range, high transparency is obtained, and the visibility of the contents is enhanced when the multilayer film is used as, for example, a packaging material, which is preferable.
  • a method for producing a multilayer film of the present disclosure is a method for producing a multilayer film of the present disclosure.
  • the method for producing the multilayer film of the present disclosure is not particularly limited, and for example, a method in which layers included as constituent components of the multilayer film of the present disclosure are mixed and adhered near the interface to form a multilayer film. is preferred.
  • Examples of such a method include a co-extrusion method in which melted resins are laminated, and a heat-sealing method in which pre-formed resin multilayer films are heat-sealed.
  • the coextrusion method in which melted resins are laminated is more preferable from the viewpoint that the interlayer adhesion strength in each layer is higher and a multilayer film in which delamination is less likely to occur can be formed.
  • the method for producing a multilayer film of the present disclosure preferably includes a step of laminating a layer containing polyolefin on a base material containing a 4-methyl-1-pentene polymer by direct lamination. This makes it possible to obtain a multilayer film in which the 4-methyl-1-pentene layer and the polyolefin layer are in contact at least partially.
  • the direct lamination method is a method of laminating a 4-methyl-1-pentene layer and a polyolefin layer in direct contact with each other.
  • the direct lamination method is a method in which the raw material of the polyolefin layer extruded from the extruder and the conveyed film containing 4-methyl-1-pentene are directly bonded and laminated. good too.
  • the film containing 4-methyl-1-pentene layer and the polyolefin layer before laminating the 4-methyl-1-pentene layer and the polyolefin layer, for example, it is preferable to subject the film containing 4-methyl-1-pentene to a surface treatment.
  • a more excellent interlayer adhesive strength can be obtained by surface treatment.
  • Examples of surface treatment include corona treatment and ozone treatment. Corona treatment can be performed using, for example, Corona Master (eg, PS-10S manufactured by Shinko Denki Co., Ltd.). Ozone treatment can be performed using a UV ozone cleaner (for example, UV42 manufactured by Nippon Laser Electronics Co., Ltd.).
  • examples of surface treatment include plasma treatment, UV treatment, and flame treatment.
  • At least one side of the layer containing the 4-methyl-1-pentene polymer is subjected to at least one treatment selected from the group consisting of plasma treatment, corona treatment, ozone treatment, UV treatment and flame treatment. is preferably applied.
  • the multilayer film of the present disclosure may be a multilayer film obtained by extrusion laminating a layer containing a polyolefin onto a layer containing a 4-methyl-1-pentene polymer.
  • the method for producing a multilayer film of the present disclosure includes a treatment step of surface-treating at least one side of a substrate containing a 4-methyl-1-pentene-based polymer, and the surface-treated surface of the substrate. and a lamination step of laminating a polyolefin on the polyolefin, wherein the interlayer adhesion strength between the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin is 0.5 N / 15 mm or more, and the polyolefin It may be a method for producing a multilayer film having a heat seal strength of 3 N/15 mm to 15 N/15 mm when the layers containing are brought into contact with each other and heat sealed.
  • the treatment step is a step of surface-treating at least one side of the substrate containing the 4-methyl-1-pentene polymer. Details such as specific aspects and preferred aspects of the surface treatment are as described above.
  • the surface treatment preferably includes at least one treatment selected from the group consisting of plasma treatment, corona treatment, ozone treatment, UV treatment and flame treatment.
  • the lamination step is a step of laminating polyolefin on the surface of the base material that has undergone the surface treatment. Details of the method for laminating polyolefin, such as specific aspects and preferred aspects, are as described above.
  • the polyolefin is subjected to ozone treatment, the ozone-treated surface of the polyolefin is brought into contact with the surface-treated surface of the base material, and the polyolefin is laminated on the surface-treated surface of the base material.
  • the lamination step is preferably a step of laminating polyolefin on a substrate containing a 4-methyl-1-pentene polymer by extrusion lamination.
  • the multilayer film of the present disclosure includes, for example, tapes, adhesive tapes, masking tapes, masking multilayer films, temporary adhesive multilayer films, freshness-preserving packaging multilayer films, plastic envelopes, easy-open packaging bags, automatic packaging multilayer films, shopping bags, Standing bags, multi-layer film containers for liquids, transparent packaging boxes, building materials, multi-layer films for bonding, multi-layer films for agriculture, food packaging materials, fruit packaging materials, flower packaging materials, electronic component packaging materials, machine component packaging materials, grain packaging materials , marine product packaging materials such as seafood, multi-layer medical films, medical tapes, plant cell culture packs, seedling storage and growth packs, animal cell culture packs, carbon dioxide separation membranes, hydrogen separation membranes, oxygenation membranes, etc. Can be used widely.
  • the container of the present disclosure is a container that includes the multilayer film of the present disclosure and is sealed by heat-sealing the layers containing the polyolefin in the multilayer film. That is, the container of the present disclosure is a container manufactured using the multilayer film of the present disclosure, and the layer containing the polyolefin in the multilayer film functions as a heat seal layer.
  • a cell culture pack of the present disclosure includes a multilayer film of the present disclosure.
  • the multilayer film of the present disclosure can be suitably used as a cell culture pack.
  • Embodiments of the present disclosure also include the following aspects.
  • a layer containing a 4-methyl-1-pentene polymer and a layer containing a polyolefin, wherein at least the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin The layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin are partially in contact, and the interlayer adhesion strength between the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin is 0.5 N/15 mm or more, and contains the polyolefin at 120 ° C.
  • the polyolefin is an unsaturated carboxylic acid-modified ethylene- ⁇ -olefin copolymer, an ethylene-unsaturated carboxylic acid-based copolymer, an ethylene-vinyl acetate copolymer, a silane-modified ethylene-vinyl acetate copolymer,
  • the multilayer film according to ⁇ 1> containing at least one selected from the group consisting of ionomers of unsaturated carboxylic acid-modified ethylene- ⁇ -olefin copolymers and ionomers of ethylene-unsaturated carboxylic acid-based copolymers.
  • ⁇ 3> The multilayer film according to ⁇ 1> or ⁇ 2>, wherein the layer containing the 4-methyl-1-pentene polymer has a thickness of 5 ⁇ m to 50 ⁇ m.
  • ⁇ 4> The multilayer film according to any one of ⁇ 1> to ⁇ 3>, wherein the layer containing the polyolefin has a thickness of 3 ⁇ m to 15 ⁇ m.
  • ⁇ 5> The multilayer film according to any one of ⁇ 1> to ⁇ 4>, which is an oxygen permeable multilayer film or a carbon dioxide permeable multilayer film.
  • the oxygen permeability is 1000 mL/m 2 ⁇ day ⁇ atm to 100000 mL/m 2 ⁇ day ⁇ atm
  • the carbon dioxide permeability is 8000 mL/m 2 ⁇ day ⁇ atm to 250000 mL/m 2 ⁇ day ⁇ atm.
  • ⁇ 7> The multilayer film according to any one of ⁇ 1> to ⁇ 6>, which has a hydrogen permeability of 10,000 mL/m 2 ⁇ day ⁇ atm to 300,000 mL/m 2 ⁇ day ⁇ atm.
  • ⁇ 8> The multilayer film according to any one of ⁇ 1> to ⁇ 7>, which has a moisture permeability of 10 g/m 2 ⁇ day to 80 g/m 2 ⁇ day.
  • ⁇ 9> The multilayer film according to any one of ⁇ 1> to ⁇ 8>, wherein unevenness is formed on the surface of the layer containing the polyolefin.
  • a cell culture pack comprising the multilayer film according to any one of ⁇ 1> to ⁇ 9>.
  • MP1 Four wrap (4-methyl-1-pentene polymer film, manufactured by Riken Fabro Co., Ltd.) In MP1, the content of the 4-methyl-1-pentene polymer is 70% by mass or more and 100% by mass or less.
  • MP2 4-methyl-1-pentene polymer film produced by the following method MP2 has a 4-methyl-1-pentene polymer content of 100% by mass.
  • TPX MX002O was put into all the single-screw extruders of the following three types of three-layer T-die molding machines, and a processing temperature of 260 ° C., a chill roll temperature of 25 ° C., and a take-up speed of 10 m / min to obtain a single layer film with a thickness of 50 ⁇ m. .
  • ⁇ Molding machine Three types of three-layer T-die molding machine with a width of 350mm equipped with a 30mm ⁇ single screw extruder, a 40mm ⁇ single screw extruder, and a 30mm ⁇ single screw extruder ⁇ TPX MX002O: 4-methyl-1-pentene polymer (manufactured by Mitsui Chemicals, Inc., MFR 23 g/10 minutes (260° C.))
  • MP3 4-methyl-1-pentene-based polymer film produced by the following method MP3 has a 4-methyl-1-pentene-based polymer content of 90% by mass and contains polybutene-1 The amount is 10% by weight.
  • Example 2 and Example 4> In the same manner as in Example 1, except that the output of corona treatment was changed to the output (kW) shown in Table 1, and the processing speed was adjusted so that the thickness of the polyolefin layer was as shown in Table 1. A multilayer film was obtained.
  • Example 3 A multilayer film was obtained in the same manner as in Example 2, except that the ozone treatment was performed in addition to the corona treatment as the surface treatment.
  • Example 5 A multilayer film was obtained in the same manner as in Example 4, except that the surface treatment was ozone treatment in addition to corona treatment.
  • Examples 6 to 8> Except that the type of 4-methyl-1-pentene polymer was changed as shown in Table 1, and the processing speed was adjusted so that the thickness of the polyolefin layer was as shown in Table 1. A multilayer film was obtained in the same manner as in Example 5.
  • the interlayer adhesion strength between the 4-methyl-1-pentene layer and the polyolefin layer was evaluated using the above-mentioned methods. method.
  • the multilayer film when the carbon dioxide permeability is 70000 mL/m 2 ⁇ day ⁇ atm or more and the oxygen permeability is 20000 mL/m 2 ⁇ day ⁇ atm or more, the multilayer film has excellent gas permeability. means.
  • the heat seal strength and interlayer adhesive strength of the multilayer film were measured.
  • the method for measuring the heat seal strength is as follows.
  • the heat seal strength was measured by preparing two multilayer films each including a layer containing the 4-methyl-1-pentene polymer and a layer containing the polyolefin.
  • the polyolefin layers of the multilayer film were opposed to each other and heat-sealed with a seal bar width of 5 mm at a heat-sealing temperature of 120° C., a pressure of 0.2 MPa, and a sealing time of 1 second, and then heat was released.
  • a 15 mm wide test piece was cut from the heat-sealed specimen, and the peel strength was measured when the heat-sealed portion was peeled off at a crosshead speed of 300 mm/min.
  • the method for measuring the interlayer adhesive strength is as follows. A test piece with a width of 15 mm was cut out from the multilayer film, and the interlayer adhesion strength was measured using a tensile tester (Autograph AG-X manufactured by Shimadzu Corporation) in accordance with JIS Z1707:1997. The interlayer adhesion strength between the 4-methyl-1-pentene layer and the polyolefin layer in the test piece was measured under the conditions of a distance between chucks of 90 mm and a tensile speed of 500 mm/min. Table 1 shows the results. In Example 5, the hydrogen permeability was 109,000 mL/m 2 ⁇ day ⁇ atm and the moisture permeability was 57 g/m 2 ⁇ day. Therefore, it was excellent in hydrogen permeability and moisture permeability. Hydrogen permeability and water vapor permeability were measured by the methods described above.
  • a layer containing a 4-methyl-1-pentene polymer and a layer containing a polyolefin are included, and a layer containing a 4-methyl-1-pentene polymer and a layer containing a polyolefin are The layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin are in contact with each other at least partially, and the interlayer adhesion strength between the layer containing the 4-methyl-1-pentene polymer and the layer containing the polyolefin is 0.5 N/15 mm or more, and the layers containing the polyolefin are separated at 120°C.
  • Each example using a multilayer film having a heat seal strength of 3 N / 15 mm to 15 N / 15 mm when heat-sealed by contacting has a carbon dioxide permeability of 70000 mL / m 2 ⁇ day ⁇ atm or more, oxygen The permeability was 20000 mL/m 2 ⁇ day ⁇ atm or more. Therefore, the multilayer film of each example was excellent in gas permeability. Moreover, the multilayer film of each example had a heat seal strength of 3 N/15 mm or more at 120° C., and thus was excellent in heat sealability at low temperatures.
  • Comparative Example 1 which does not contain a polyolefin layer, could not be heat-sealed. In Comparative Examples 2 and 3, in which the interlayer adhesive strength was not 0.5 N/15 mm or more, the layers did not adhere to each other, and a multilayer film could not be obtained.

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Abstract

Film multicouche qui comprend une couche contenant un polymère de 4-méthyl-1-pentène et une couche contenant une polyoléfine, la couche contenant un polymère de 4-méthyl-1-pentène et la couche contenant une polyoléfine étant au moins partiellement en contact l'une avec l'autre ; la force de liaison intercouche entre la couche contenant un polymère de 4-méthyl-1-pentène et la couche contenant une polyoléfine est de 0,5 N/15 mm ou plus; et la résistance de thermoscellage est de 3N/15 mm à 15 N/15 mm si des couches contenant une polyoléfine sont mises en contact l'une avec l'autre et thermoscellées à 120 °C.
PCT/JP2022/008633 2021-03-02 2022-03-01 Film multicouche, récipient, emballage pour culture cellulaire et procédé de production de film multicouche WO2022186208A1 (fr)

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US18/278,147 US20240123716A1 (en) 2021-03-02 2022-03-01 Multilayer film, container, pack for cell culture and method for producing multilayer film
CN202280013851.2A CN116887984A (zh) 2021-03-02 2022-03-01 多层膜、容器、细胞培养用包装和多层膜的制造方法
JP2023503868A JPWO2022186208A1 (fr) 2021-03-02 2022-03-01
EP22763263.5A EP4302997A1 (fr) 2021-03-02 2022-03-01 Film multicouche, récipient, emballage pour culture cellulaire et procédé de production de film multicouche

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